CN112962111A - Method for electrochemically synthesizing isocoumarin compounds - Google Patents
Method for electrochemically synthesizing isocoumarin compounds Download PDFInfo
- Publication number
- CN112962111A CN112962111A CN202110150642.XA CN202110150642A CN112962111A CN 112962111 A CN112962111 A CN 112962111A CN 202110150642 A CN202110150642 A CN 202110150642A CN 112962111 A CN112962111 A CN 112962111A
- Authority
- CN
- China
- Prior art keywords
- synthesizing
- isocoumarins
- phenyl
- compound according
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method for synthesizing isocoumarin compounds by electrochemical oxidative dehydrogenation coupling, belonging to the technical field of organic chemistry. In a non-separation electrolytic cell, carrying out constant-current electrolytic reaction on substituted aryl formic acid 1 and an alkyne compound 2 in an organic solvent in the presence of an iridium catalyst and an additive to obtain an isocoumarin derivative 3; in the invention, under the condition of electric anodic oxidation and under the catalysis of transition metal iridium, C-O/O-H bond cyclization products are obtained with high selectivity; the method has the advantages of mild reaction conditions, environmental friendliness, high yield and high purity, and provides a simple and effective synthesis way for isocoumarin compounds.
Description
Technical Field
The invention relates to a preparation method of an isocoumarin derivative, in particular to a method for synthesizing isocoumarin compounds by electrochemical oxidative dehydrogenation coupling, belonging to the field of organic chemistry.
Background
Isocoumarins are an important class of natural lactones, found in a variety of natural products, with a variety of biological activities, such as antifungal, antitumor, antiallergic, antimicrobial, anti-inflammatory, and anticancer activities. Isocoumarin is also an essential intermediate in the synthesis of many other compounds such as isoquinoline, isocarbutantin and isochromanone.
The traditional method for synthesizing the compound adopts transition metal catalyzed cyclization of ortho-halogenated aromatic ester or carboxylic acid with pi electron component. Among the methods reported in the prior literature, the direct oxidative cyclization reaction of alkyne and weakly coordinated benzoic acid catalyzed by transition metal (Rh, Ir, Ru) is considered to be an effective method for synthesizing isocoumarin with high atom economy. These transformation methods also provide a new route to break bonds for retrosynthetic analysis, however, require the use of additional equivalents of chemical oxidants (usually PhI (OAc))2/AgCO3/AgOAc, etc.) becomes a disadvantage in practical applications because these oxidants produce large amounts of by-products, pollute the environment, are poorly atomic, or are expensive, etc.
Therefore, in constructing a C-H bond functionalized reaction system related to natural products such as isocoumarin, the development of a novel green oxidation system is a problem which is addressed by chemists.
Angew. chem.int.Ed.2018,57,581 reports the application of the electroanodization technique to Ru (III) -catalyzed C-O/O-H bond cyclization of aryl groups to construct isocoumarin backbones. However, the method can only be applied to substrates with specific structures, and has certain substrate limitations.
Disclosure of Invention
In order to overcome the problems existing in the prior art: 1) poor selectivity of aryl carboxylic acid C-H bond with weak coordination, 2) use of a large amount of oxidant and the like, and the invention discloses a preparation method of a novel isocoumarin compound; the preparation method can obtain a C-O/O-H bond cyclization product with high selectivity under the condition of electric anodic oxidation and under the catalysis of transition metal iridium; the method has the advantages of mild reaction conditions, environmental friendliness, high yield, good purity and suitability for industrial production.
The invention provides a method for synthesizing isocoumarin compounds, which comprises the following steps: in a non-separation electrolytic cell, carrying out constant-current electrolytic reaction on substituted aryl formic acid 1 and an alkyne compound 2 in an organic solvent in the presence of an iridium catalyst and an additive to obtain an isocoumarin derivative 3; the reaction equation is as follows:
wherein, in the substituted aryl formic acid, Ar of the substituted aryl is selected from phenyl, substituted phenyl, naphthyl, indole, azomethylindole, furan, thiophene, benzothiophene and the like, and the substituent in the substituted phenyl is selected from one or more of C1-C4 alkyl, C1-C4 alkoxy, halogen, hydroxymethyl, phenyl, nitrile group, nitro, trifluoromethyl and C1-C4 alkoxycarbonyl;
R1、R2each independently selected from C1-C4 alkyl, phenyl, substituted phenyl, trifluoromethyl, CR3R4(OH), C1-C4 alkyl with halogen/phenyl/hydroxy/TBSO substitution, thiophene,And the like, wherein the substituent in the substituted phenyl is one or more of C1-C4 alkyl, C1-C4 alkoxy, halogen, hydroxymethyl, phenyl, nitrile group, nitro, trifluoromethyl and C1-C4 alkoxycarbonyl; r3And R4Each independently selected from C1-C4 alkyl or trifluoromethyl, or R3, R4 together form a 4-8 membered cyclic alkane.
In the above substituents, the halogen is selected from fluorine, chlorine, bromine or iodine.
Typical substituted arylcarboxylic acid 1 compounds have the following structure:
typical acetylenic compounds 2 are of the structure:
further, in the above technical solution, the organic solvent is selected from a nitrile solvent (e.g., acetonitrile) and/or an alcohol solvent (e.g., methanol). Methanol solvent is preferred.
Further, in the above technical solution, the iridium catalyst is selected from iridium catalysts commonly used in this type of reaction in the art, such as (Cp × IrCl)2)2。
Further, in the above technical scheme, the additive is selected from n-Bu4NI (tetrabutyl ammonium iodide), n-Et4NOAc (tetrabutylammonium acetate), n-Et4NBF4(tetrabutylammonium tetrafluoroborate), n-Et4NI (tetraethyl ammonium iodide), NH4I. One or more of KI, NaI, KOPiv or NaOAc, more preferably n-Et4NOAc。
Further, in the above technical solution, the constant current means that the magnitude of the current output by the power supply is constant, and the output current of the constant current is the output current that is conventional in the reactions in this kind of field, for example, 1.5 to 20mA (preferably, 2.0 mA).
Further, in the technical scheme, the molar ratio of the substituted aryl formic acid 1 to the acetylene compound 2 to the iridium catalyst to the additive is 1-2: 1-2: 0.01-0.03: 1-3.
Further, in the above technical solution, the constant current electrolysis reaction temperature is selected from 30-80 ℃.
Further, in the above technical scheme, in the constant current electrolytic reaction, the progress of the reaction can be monitored by a conventional monitoring method in the art (such as TLC, HPLC or NMR), and the disappearance or no longer reaction of the compound 1 is generally used as a reaction endpoint.
Further, in the above technical scheme, after the reaction is finished, if a crude compound is obtained, the crude compound can be separated and purified by conventional means such as preparative HPLC, preparative TLC or recrystallization.
The positive progress effects of the invention are as follows: the preparation method can avoid using conventional expensive oxidant, can obtain the selective cyclized isocoumarin derivative product, has high yield and good purity, and is more suitable for industrial production.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Drawings
FIG. 1 is a single crystal diffraction pattern of the product obtained in 3-1 of example 3.
Example 1
Condition optimization experiment
Reaction conditions are as follows: 1a (0.2mmol), 2a (0.24mmol), (Cp IrCl)2)2(3 mol%) screening of different additives, temperatures, currents and solvents
Finally, determining the optimal conditions: compound 1(0.24mmol), compound 2(0.20mmol), (Cp × IrCl)2)2(3mol%)、n-Bu4OAc (3equiv), MeOH (3ml), 1.5mA were reacted at 60 ℃ for 12 h.
Example 2
Example 2-1
In the non-dispensingBenzoic acid 1a (32.6mg,0.24mmol), tolane 2a (35.6mg,0.2mmol), (Cp IrCl) were added to the electrolytic cell in sequence2)2(3 mol%) (4.8mg,0.02mmol), tetrabutylammonium acetate (180.9mg,0.6mmol) and methanol (3 mL). Then platinum sheets (1.5X 1.0 cm) are added on the cathode and anode respectively2) The electrodes were charged with 1.5mA of current and the electrolysis was continued at 60 ℃ for 12 hours. After the reaction was completed, the solvent was suspended under reduced pressure and then isolated and purified by silica gel column chromatography (hexane/EtOAc:40/1) to give 3a (55.9mg, yield 90%, purity > 95%) as a colorless solid.1H NMR(600MHz,CDCl3):δ7.50–7.45(m,1H),7.44–7.38(m,3H),7.35–7.28(m,3H),7.24–7.16(m,5H),7.01–6.99(m,1H),2.91(s,3H).13C NMR(150MHz,CDCl3):δ161.7,150.8,143.6,140.6,135.1,133.9,133.2,131.5,131.2,129.2,129.2,128.9,128.2,128.0,123.80,119.1,117.1,23.7.
Examples 2 to 2
From 2c (22.0mg,0.2mmol), 3cc (41.9mg, yield 91%, purity greater than 95%) of a white solid was obtained under the same reaction conditions as above.1H NMR(600MHz,CDCl3):δ8.28(d,J=7.8Hz,1H),7.69(t,J=7.8Hz,1H),7.49(d,J=8.4Hz,1H),7.42(t,J=7.2Hz,1H),2.58–2.53(m,4H),1.75–1.69(m,2H),1.60–1.53(m,2H),1.01(t,J=7.2Hz,3H),0.97(t,J=7.8Hz,3H).13C NMR(150MHz,CDCl3):δ162.9,154.2,138.0,134.6,129.8,127.1,122.7,120.8,112.3,32.7,28.2,22.9,21.2,14.2,13.8.
Examples 2 to 3
As in the above reaction conditions, from 2s (43.2mg,0.2mmol), 3s (48.3mg, yield 69%, purity > 95%) was obtained as a colorless oily liquid.1H NMR(400MHz,CDCl3):δ8.10(d,J=8.4Hz,2H),7.62–7.59(m,3H),7.46(d,J=8.0Hz,1H),7.30(d,J=7.2Hz,1H),3.92(s,3H),2.83(s,3H),2.60(t,J=7.6Hz,2H),1.62–1.54(m,2H),1.37–1.27(m,2H),0.85(t,J=7.2Hz,3H).13C NMR(100MHz,CDCl3):δ166.4,161.2,149.9,143.8,138.9,137.8,133.9,131.2,130.5,129.4,129.0,121.6,119.7,114.8,52.2,31.9,26.8,23.6,22.6,13.7.
By changing the reaction conditions of the above example 2 and the reaction substrate, different compounds 3 were obtained, and the reaction results were as follows:
example 3
Example 3-1
In a non-partitioned electrolytic cell were added sequentially the benzoic acid substrate 1a (32.7mg,0.24mmol), the alkynol 2aa (32.0mg,0.2mmol), (Cp IrCl)2)2(3 mol%) (4.8mg,0.02mmol), tetrabutylammonium acetate (180.9mg,0.6mmol) and methanol (3 mL). Then platinum sheets (1.5X 1.0 cm) are added on the cathode and anode respectively2) The electrodes were charged with 1.5mA of current and the electrolysis was continued at 60 ℃ for 12 hours. After the reaction was completed, the solvent was suspended under reduced pressure and then isolated and purified by silica gel column chromatography (hexane/EtOAc:10/1) to give the product as a white solid (44.1mg, yield 75%, purity > 95%).1H NMR(600MHz,CDCl3):δ7.50–7.44(m,3H),7.39(t,J=7.2Hz,1H),7.29–7.27(m,3H),6.63(d,J=7.8Hz,1H),2.87(s,3H),2.01(s,1H),1.46(s,6H).13C NMR(150MHz,CDCl3) Delta 161.2,156.6,143.4,141.3,135.1,133.9,131.1,131.0,129.1,128.5,123.7,118.7,114.4,73.4,30.0,23.6. the single crystal diffractogram of this compound is shown in FIG. 1.
Examples 3 to 2
Under the same reaction conditions as above, replacing the alkynol, starting from 2gg (38.3mg,0.2mmol), colorless solid 3s (51.3mg, yield 81%, purity greater than 95%) can be obtained m.p. 152.4-165.5 ℃.1H NMR(600MHz,CDCl3):δ7.65–7.62(m,1H),7.54–7.52(m,1H),7.35–7.34(m,1H),3.41(s,1H),3.08(s,1H),2.81–2.78(m,4H),1.89(s,3H),1.57–1.56(m,2H),1.52–1.47(m,2H),0.97(t,J=7.2Hz,3H).13C NMR(150MHz,CDCl3):δ160.6,146.5,143.9,139.7,134.2,131.8,125.2(q,J=S52 286.9Hz),122.0,119.9,118.6,76.4(t,J=30.2Hz),32.5,25.8,23.7,23.3,23.0,14.0.19F NMR(565MHz,CDCl3):-80.50.HRMS(ESI-TOF)m/z Calcd for C17H20F3O3[M+H]+329.1359,found 329.1351.
Examples 3 to 3
By replacing the alkynol with the above reaction conditions, a yellow solid was obtained starting from 2dd (38.0mg,0.2mmol) for 6h (55.7mg, yield 86%, purity > 95%). M.p. 107.4-111.8 ℃.1H NMR(600MHz,CDCl3):δ7.40(t,J=7.2Hz,1H),7.28–7.24(m,1H),7.19–7.18(m,2H),7.02–7.01(m,2H),6.68(d,J=7.8Hz,1H),3.87(s,3H),2.86(s,3H),2.13(s,1H),1.45(s,6H).13C NMR(150MHz,CDCl3):δ161.1,159.7,156.9,143.3,141.7,133.8,132.1,131.0,126.6,123.7,118.6,114.5,114.0,73.4,55.5,30.0,23.5.HRMS S50(ESI-TOF)m/z Calcd for C20H21O4[M+Na]+347.1254,found 347.1246.
By changing the reaction conditions of the above example 3 and the reaction substrate, different compounds 3 were obtained, and the reaction results were as follows:
example 4
Entry | A:B | (Cp*IrCl2)2 | Solvent | Temp. | Time | Yielda |
1 | 1.2:1 | 3mol% | MeOH | 60℃ | 12h | 37% |
2 | 1.2:1 | 3mol% | MeOH | 50℃ | 12h | 43% |
3 | 1.2:1 | 3mol% | CF3CH2OH | 50℃℃ | 12h | 58% |
4 | 1.2:1 | 3mol% | CF3CH2OH | 50℃ | 10h | 50% |
5 | 1:1.5 | 3mol% | CF3CH2OH | 50℃ | 12h | 64% |
6 | 1:2 | 3mol% | CF3CH2OH | 50℃ | 12h | 68% |
7 | 1:2 | 5mol% | CF3CH2OH | 50℃ | 10h | 96% |
aYield was determined by1H NMR with CH2Br2 as the internal standard.
Example 5
In a non-partitioned electrolytic cell were added benzoic acid 1b (24.4mg,0.2mmol), alkynyl substrate 2hh (68.0mg,0.4mmol), (Cp IrCl) in sequence2)2(5 mol%) (8.0mg,0.02mmol), tetrabutylammonium acetate (180.9mg,0.6mmol) and trifluoroethanol (3 mL). Then platinum sheets (1.5X 1.0 cm) are added on the cathode and anode respectively2) The electrodes were charged with 1.5mA of current and the electrolysis was continued at 50 ℃ for 10 hours. After the reaction was completed, the solvent was suspended under reduced pressure and then isolated and purified by silica gel column chromatography (hexane/EtOAc:50/1) to give a white solid product (45.8mg, yield 79%, purity > 95%).1H NMR(600MHz,CDCl3):δ8.41(d,J=7.8Hz,1H),7.71–7.64(m,2H),7.53–7.48(m,3H),7.33–7.27(m,2H),7.06(d,J=7.8Hz,1H).13C NMR(150MHz,CDCl3):δ159.5,138.9(q,J=36.0Hz),137.1,135.2,130.5,130.4,129.9,129.8,129.1,128.7,126.9,121.6,121.0(q,J=2.8Hz),119.2(q,J=274.6Hz).19F NMR(565MHz,CDCl3):δ-63.17.
Under the same conditions as above, starting from 1f (30.0mg,0.2mmol), a white solid product (54.1mg, 85% yield, greater than 95% purity) was obtained.1H NMR(600MHz,CDCl3):δ8.18(s,1H),7.47–7.42(m,3H),7.31–7.30(m,3H),2.44(s,3H),1.66(s,3H).13C NMR(150MHz,CDCl3):δ160.3,141.1,140.7,138.4(q,J=34.5Hz),137.5,133.3,131.2,130.5,130.5,128.9(d,J=24.0Hz),128.4,122.6,121.4(q,J=3.0Hz),119.6(q,J=274.9Hz),22.6,21.0.19F NMR(565MHz,CDCl3):δ-61.28.
By changing the reaction substrate under the reaction conditions of the above example 5, different compounds 3 were obtained, and the reaction results were as follows:
the foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (9)
1. A method for synthesizing isocoumarin compounds is characterized by comprising the following steps: in a non-separation electrolytic cell, carrying out constant-current electrolytic reaction on substituted aryl formic acid 1 and an alkyne compound 2 in an organic solvent in the presence of an iridium catalyst and an additive to obtain an isocoumarin derivative 3; the reaction equation is as follows:
in the substituted aryl formic acid, Ar of the substituted aryl is selected from phenyl, substituted phenyl, naphthyl, indole, azomethylindole, furan, thiophene or benzothiophene, and the substituent in the substituted phenyl is selected from one or more of C1-C4 alkyl, C1-C4 alkoxy, halogen, hydroxymethyl, phenyl, nitrile group, nitro, trifluoromethyl and C1-C4 alkoxycarbonyl;
R1、R2each independently selected from C1-C4 alkyl, phenyl, substituted phenyl, trifluoromethyl, CR3R4(OH), C1-C4 alkyl with halogen/phenyl/hydroxy/TBSO substitution, thiophene orThe substituent in the substituted phenyl is selected from one or more of C1-C4 alkyl, C1-C4 alkoxy, halogen, hydroxymethyl, phenyl, nitrile group, nitro, trifluoromethyl and C1-C4 alkoxycarbonyl; r3And R4Each independently selected from C1-C4 alkyl or trifluoromethyl, or R3,R4Together form a 4-8 membered cyclic alkane.
2. The method of synthesizing isocoumarins compound according to claim 1, wherein: the halogen is selected from fluorine, chlorine, bromine or iodine.
3. The method of synthesizing isocoumarins compound according to claim 1, wherein: the organic solvent is selected from nitrile solvents and/or alcohol solvents.
4. The method of synthesizing isocoumarins compound according to claim 1, wherein: said iridium catalyst is selected from (CpIrCl)2)2。
5. The method of synthesizing isocoumarins compound according to claim 1, wherein: the additive is selected from n-Et4NOAc, KOPiv or NaOAc.
6. The method of synthesizing isocoumarins compound according to claim 6, wherein: the additive is selected from n-Et4NOAc。
7. The method of synthesizing isocoumarins compound according to claim 1, wherein: the constant current means that the magnitude of current output by the power supply is constant, and the output current of the constant current is 1.5-20 mA.
8. The method of synthesizing isocoumarins compound according to claim 1, wherein: the molar ratio of the substituted aryl formic acid 1 to the alkyne compound 2 to the iridium catalyst to the additive is 1-2: 1-2: 0.01-0.03: 1-3.
9. The method of synthesizing isocoumarins compound according to claim 1, wherein: the constant-current electrolytic reaction temperature is selected from 30-80 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110150642.XA CN112962111A (en) | 2021-02-02 | 2021-02-02 | Method for electrochemically synthesizing isocoumarin compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110150642.XA CN112962111A (en) | 2021-02-02 | 2021-02-02 | Method for electrochemically synthesizing isocoumarin compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112962111A true CN112962111A (en) | 2021-06-15 |
Family
ID=76274614
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110150642.XA Withdrawn CN112962111A (en) | 2021-02-02 | 2021-02-02 | Method for electrochemically synthesizing isocoumarin compounds |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112962111A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113388852A (en) * | 2021-07-26 | 2021-09-14 | 河南师范大学 | Method for synthesizing polysubstituted pyrido [1,2-e ] purine compound by electrochemical dehydrogenation coupling |
CN114539197A (en) * | 2022-03-03 | 2022-05-27 | 浙江工业大学 | Synthetic method of 3-fluoroalkyl substituted chromone derivative |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101062926A (en) * | 2005-12-14 | 2007-10-31 | 南开大学 | Preparation and usage of unnatural 3,4-dihydro isocoumarin derivatives |
CN103224482A (en) * | 2013-04-10 | 2013-07-31 | 上海交通大学 | Isocoumarin compound, derivatives and synthesis method thereof |
CN106588851A (en) * | 2016-11-29 | 2017-04-26 | 南阳师范学院 | Method of synthesizing isocoumarin derivatives by catalyzing tandem reaction in water phase |
CN112126942A (en) * | 2020-10-09 | 2020-12-25 | 中国药科大学 | Method for realizing secondary arylamine N-N coupling by using electrochemical reaction |
-
2021
- 2021-02-02 CN CN202110150642.XA patent/CN112962111A/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101062926A (en) * | 2005-12-14 | 2007-10-31 | 南开大学 | Preparation and usage of unnatural 3,4-dihydro isocoumarin derivatives |
CN103224482A (en) * | 2013-04-10 | 2013-07-31 | 上海交通大学 | Isocoumarin compound, derivatives and synthesis method thereof |
CN106588851A (en) * | 2016-11-29 | 2017-04-26 | 南阳师范学院 | Method of synthesizing isocoumarin derivatives by catalyzing tandem reaction in water phase |
CN112126942A (en) * | 2020-10-09 | 2020-12-25 | 中国药科大学 | Method for realizing secondary arylamine N-N coupling by using electrochemical reaction |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113388852A (en) * | 2021-07-26 | 2021-09-14 | 河南师范大学 | Method for synthesizing polysubstituted pyrido [1,2-e ] purine compound by electrochemical dehydrogenation coupling |
CN113388852B (en) * | 2021-07-26 | 2022-07-15 | 河南师范大学 | Method for synthesizing polysubstituted pyrido [1,2-e ] purine compound by electrochemical dehydrogenation coupling |
CN114539197A (en) * | 2022-03-03 | 2022-05-27 | 浙江工业大学 | Synthetic method of 3-fluoroalkyl substituted chromone derivative |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112962111A (en) | Method for electrochemically synthesizing isocoumarin compounds | |
CN112877721A (en) | Method for synthesizing isocoumarin compounds by electrochemical oxidative dehydrogenation coupling | |
CN111777637A (en) | Axial chiral oxindole-derived styrene phosphine oxide catalyst and preparation method and application thereof | |
CN108690007B (en) | C-H coupling reaction catalyzed by transition metal for efficiently preparing o-cyanoated aromatic ring or unsaturated aliphatic ring compound | |
Tian et al. | Phosphine‐Catalyzed Annulations between Modified Allylic Derivatives and Polar Dienes and Substituent Effect on the Annulation Mode | |
CN114892187A (en) | Method for electrochemically synthesizing imidazole polycyclic aromatic compounds | |
CN112824422A (en) | Chiral ferrocene-indole diphosphine ligand as well as preparation method and application thereof | |
Ye et al. | Gorlos-Phos: Addressing the stereoselectivity in palladium-catalyzed exo-mode cyclization of allenes with a nucleophilic functionality | |
CN111808023B (en) | Method for preparing 3-aryl isoquinoline derivative | |
CN103664821B (en) | A kind of benzothiazole compound preparation method based near amino thiophenols cyclisation | |
CN113200914A (en) | Alkynylated tetrahydroisoquinoline compound and preparation method and application thereof | |
WO2024017221A1 (en) | SYNTHESIS METHOD FOR α-AZIDO KETONE CONTAINING TERTIARY STEREOCENTER | |
CN114574882A (en) | Method for synthesizing ortho-alkyl aryl pyridine compound by electrochemical oxidative dehydrogenation coupling | |
CN108558944B (en) | Preparation method of 4-phosphoryl-1, 4, 5-trisubstituted 1,2, 3-triazole | |
CN111303096B (en) | Synthesis method of polysubstituted 1, 3-dihydronaphtho [2,3-c ] furan derivative | |
CN113957461B (en) | Electrochemical synthesis method of 1,1' -binaphthyl compound | |
JP3912818B2 (en) | Process for producing chiral α-halogen carboxylic acid | |
CN109503387B (en) | Method for catalyzing asymmetric synthesis of binaphthyl diamine | |
CN108586457B (en) | indole carbocycle dearomatization synthesis method based on nitrogen atom α hydrogen migration strategy | |
CN106854125B (en) | Method for preparing α -fluoro- β -ethynyl ketone compound containing two chiral centers | |
CN113980055B (en) | Cyclic phosphonamide derivative with biaryl framework, synthesis method and application | |
Hua et al. | Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines | |
CN114214650B (en) | Synthesis method of electrochemical oxidation beta-thiocyano substituted enamide compound | |
CN114959750B (en) | Method for preparing (E) -2, 2-difluoro-4-phenylbut-3-ethyl enoate compound by electrocatalytic | |
CN109912467A (en) | A kind of synthetic method of 2- aryl phenylethylamine derivative |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210615 |
|
WW01 | Invention patent application withdrawn after publication |